JP6167680B2 - Colored photosensitive resin composition - Google Patents

Description

  The present invention relates to a colored photosensitive resin composition.

  The colored photosensitive resin composition is used, for example, for producing a color filter such as a liquid crystal display device or a solid-state imaging device. As such a colored photosensitive resin composition, a colored photosensitive resin composition containing a thiazole dye as a colorant and an alkali-soluble resin having a phenolic hydroxyl group as a binder resin is known (Patent Document 1). .

JP 2008-242325 A

  The color filter obtained from the conventionally known colored photosensitive resin composition has not always been sufficiently satisfactory in lightness.

［式（Ａ−Ｉ）中、Ｘは、窒素原子またはＣＨを示し、Ｒ^４１は、水素原子または炭素数１〜４のアルキル基を示し、Ｒ^４２は、水素原子、シアノ基、カルバモイル基、カルボキシル基または炭素数１〜４のアルコキシカルボニル基を示し、Ｒ^４３は、酸素原子、Ｃ（ＣＮ）₂、Ｃ（ＣＮ）ＣＯＯＬ^１またはＣ（ＣＯＯＬ^１）₂を示し、Ｌ^１は、炭素数１〜８のアルキル基を示し、Ｌ^１がメチレン単位を有する場合には、該メチレン単位の１つまたは２つが酸素原子で置換されていてもよく、Ｒ^４４〜Ｒ^４６は、それぞれ独立して、水素原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよいアミノ基、炭素数１〜２０のアルキル基であって、該アルキル基を構成するメチレン基間に酸素原子が挿入されているアルキル基、置換されていてもよいアリール基、またはヒドロキシル基を示す。］
［２］ アルカリ可溶性樹脂（Ｂ）が、不飽和カルボン酸及び不飽和カルボン酸無水物からなる群から選ばれる少なくとも１種の単量体（ａ）に由来する構成単位と、炭素数２〜４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）に由来する構成単位とを含む共重合体である［１］に記載の着色感光性樹脂組成物。
［３］ 環状エーテル構造が、脂肪族多環式エポキシ構造である［１］又は[２]に記載の着色感光性樹脂組成物。
［４］ 炭素数２〜４の環状エーテル構造とエチレン性不飽和結合とを有する単量体（ｂ）が、式（ＩＩ）で表される化合物及び式（ＩＩＩ）で表される化合物からなる群から選ばれる少なくとも１種の化合物である[１]〜[３]のいずれかに記載の着色感光性樹脂組成物。

［式（ＩＩ）及び式（ＩＩＩ）中、Ｒ^b1及びＲ^b2は、水素原子、又は炭素数１〜４のアルキル基を表し、該アルキル基に含まれる水素原子は、ヒドロキシ基で置換されていてもよく、
Ｘ^b1及びＸ^b2は、単結合、−Ｒ^b3−、＊−Ｒ^b3−Ｏ−、＊−Ｒ^b3−Ｓ−又は＊−Ｒ^b3−ＮＨ−を表し、
Ｒ^b3は、炭素数１〜６のアルカンジイル基を表し、
＊は、Ｏとの結合手を表す。］
［５］ ［１］〜［４］のいずれかに記載の着色感光性樹脂組成物により形成されるカラーフィルタ。
［６］ ［５］記載のカラーフィルタを含む表示装置。
［７］ 式（Ａ−ＩＩ）で表される化合物。

［式（Ａ−ＩＩ）中、Ｘは、窒素原子またはＣＨを示す。Ｒ^４１は、水素原子または炭素数１〜４のアルキル基を示す。Ｒ^４２は、水素原子、シアノ基、カルバモイル基、カルボキシル基または炭素数１〜４のアルコキシカルボニル基を示す。Ｒ^４３は、酸素原子、Ｃ（ＣＮ）_２、Ｃ（ＣＮ）ＣＯＯＬ^１またはＣ（ＣＯＯＬ^１）_２を示し、Ｌ^１は、炭素数１〜８のアルキル基を示す。但しＬ^１がメチレン単位を有する場合には、該メチレン単位の１つまたは２つが酸素原子で置換されていてもよい。Ｒ^６１は、水素原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、炭素数１〜２０のアルキル基であって、該アルキル基を構成するメチレン基間に酸素原子が挿入されているアルキル基、または置換されていてもよいアリール基を表す。Ｒ^６２は、水素原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよいアミノ基、または置換されていてもよいアリール基を表す。Ｒ^６３は１つ以上のハロゲン原子を有する炭素数６〜２０のアリール基を表す。］
［８］ Ｒ^６３が、式（Ａ−ＩＩＩ）で表される基である［７］記載の化合物。

［式（Ａ−ＩＩＩ）中、Ｒ^６４はハロゲン原子を表す。Ｒ^６５〜Ｒ^６７は、それぞれ独立して、水素原子、ハロゲン原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよいアミノ基、炭素数１〜２０のアルキル基であって、該アルキル基を構成するメチレン基間に酸素原子が挿入されているアルキル基、置換されていてもよいアリール基、あるいはヒドロキシル基を表す。Ｒ^６８は水素原子またはハロゲン原子を表す。］ [1] A colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E) are contained, and the colorant (A) is represented by the formula (AI And the alkali-soluble resin (B) is derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A colored photosensitive resin composition which is a copolymer containing units.

[In the formula (AI), X represents a nitrogen atom or CH, R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴² represents a hydrogen atom, a cyano group, a carbamoyl group, A carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms; R ⁴³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ ; and L ¹ represents a carbon number 1 to 8 alkyl groups, and when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom, and R ^{44 to} R ⁴⁶ are each independently , A hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an amino group which may be substituted, or an alkyl group having 1 to 20 carbon atoms, Methylene An alkyl group having an oxygen atom inserted between the groups, an aryl group which may be substituted, or a hydroxyl group is shown. ]
[2] A structural unit derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and an alkali-soluble resin (B) having 2 to 4 carbon atoms. The colored photosensitive resin composition according to [1], which is a copolymer containing a structural unit derived from the monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond.
[3] The colored photosensitive resin composition according to [1] or [2], wherein the cyclic ether structure is an aliphatic polycyclic epoxy structure.
[4] The monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond comprises a compound represented by the formula (II) and a compound represented by the formula (III). The colored photosensitive resin composition according to any one of [1] to [3], which is at least one compound selected from the group.

[In Formula (II) and Formula (III), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You can,
X ^b1 and X ^b2 represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or * -R ^b3 -NH- the stands,
R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms,
* Represents a bond with O. ]
[5] A color filter formed from the colored photosensitive resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].
[7] A compound represented by formula (A-II).

[In the formula (A-II), X represents a nitrogen atom or CH. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms. R ⁴³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents an alkyl group having 1 to 8 carbon atoms. However, when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom. R ⁶¹ is a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom, and an alkyl group having 1 to 20 carbon atoms, between the methylene groups constituting the alkyl group. It represents an alkyl group having an oxygen atom inserted therein or an aryl group which may be substituted. R ⁶² represents a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or an aryl group that may be substituted. R ⁶³ represents an aryl group having 6 to 20 carbon atoms having one or more halogen atoms. ]
[8] The compound according to [7], wherein R ⁶³ is a group represented by the formula (A-III).

[In the formula (A-III), R ⁶⁴ represents a halogen atom. R ^{65 to} R ⁶⁷ are each independently a hydrogen atom, a halogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or a carbon number. 1 to 20 alkyl groups each representing an alkyl group having an oxygen atom inserted between methylene groups constituting the alkyl group, an optionally substituted aryl group, or a hydroxyl group. R ⁶⁸ represents a hydrogen atom or a halogen atom. ]

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring photosensitive resin composition which can manufacture a high brightness color filter.

The colored photosensitive resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
The colorant (A) includes a compound represented by the formula (AI).
The colored photosensitive resin composition of the present invention preferably further contains a leveling agent (F).
The colored photosensitive resin composition of the present invention preferably further contains a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
As the colorant (A), a thiazole dye represented by the formula (AI) (hereinafter may be referred to as “dye (AI)”) may be used alone, or another dye (A1). , Pigment (P), or a mixture thereof.

In the formula (AI), preferred X is a nitrogen atom.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a t-butyl group. Preferable R ⁴¹ is an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.

The alkoxycarbonyl group having 1 to 4 carbon atoms represented by R ^42, a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, such as t- butoxycarbonyl group Can be mentioned. Preferred R ⁴² is a cyano group.

好ましいＲ^４３は酸素原子である。 Specific examples of L ¹ include groups represented by the following formulas. In the following formula, * represents a bond.

Preferable R ⁴³ is an oxygen atom.

Examples of the alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom represented by R ^{44 to} R ⁴⁶ include groups represented by the following formulae. In the following formula, * represents a bond.

Examples of the optionally substituted amino group represented by R ^{44 to} R ⁴⁶ include an amino group and a group represented by the following formula. In the following formula, * represents a bond.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^{44 to} R ⁴⁶ and having an oxygen atom inserted between methylene groups constituting the alkyl group include groups represented by the following formulae: It is done. In the following formula, * represents a bond.

Examples of the optionally substituted aryl group represented by R ^{44 to} R ⁴⁶ include groups represented by the following formulae. In the following formula, * represents a bond.

Preferred R ⁴⁴ is a methyl group, an ethyl group, or a dialkylmethyl group having 3 to 20 carbon atoms (preferably 4 to 10 carbon atoms) (particularly a di-linear alkylmethyl group). Preferred R ⁴⁵ is an amino group substituted with two alkyl groups having 1 to 10 carbon atoms (more preferably an alkyl group having 3 to 6 carbon atoms), particularly N-diisopropylamino group, N, N-di- an n-butylamino group, an N, N-di-n-pentylamino group, and an N, N-di-n-hexylamino group. Preferred R ⁴⁶ is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a naphthyl group, a phenyl group, one or more halogen atoms (preferably a fluorine atom, a chlorine atom, etc.). And more preferably a hydrogen atom, a branched alkyl group having 3 to 4 carbon atoms (preferably isopropyl group, isopentyl group, tert-butyl group), phenyl group, or chlorophenyl group.

  More specific examples of these dyes (AI) include pigments represented by formulas (AI-1) to (AI-6).

The dye (AI) can be produced, for example, by the method described in Patent Document 2 (Japanese Patent No. 2839675).

［式（Ｂ−Ｉ）及び式（Ｃ−Ｉ）中、Ｒ^４１〜Ｒ^４６は、それぞれ上記と同じ意味を表す。］ Specifically, the dye (AI) is prepared by reacting the compound represented by the formula (BI) with the compound represented by the formula (CI) in the presence of an organic solvent or without a solvent. ) Can be manufactured.

[In formula (BI) and formula (CI), R ^{41 to} R ⁴⁶ each represent the same meaning as described above. ]

［式（Ｂ−ＩＩ）及び式（Ｃ−ＩＩ）中、Ｒ^４１〜Ｒ^４６は、それぞれ上記と同じ意味を表す。］ In addition, the dye (A-I) can also be obtained by reacting the compound represented by the formula (B-II) with the compound represented by the formula (C-II) in the presence of an organic solvent or without a solvent. It can also be manufactured.

[In Formula (B-II) and Formula (C-II), R ^{41 to} R ⁴⁶ each represent the same meaning as described above. ]

［式（Ｂ−ＩＩＩ）中、Ｒ^４５〜Ｒ^４６は、それぞれ上記と同じ意味を表す。］ The dye (A-I) can also be obtained by reacting the compound represented by the formula (B-III) with the compound represented by the formula (C-II) in the presence of an organic solvent or without a solvent. It can also be manufactured.

[In the formula (B-III), R ^{45 to} R ⁴⁶ each have the same meaning as described above. ]

［式（Ｃ−ＩＩＩ）中、Ｒ^４１〜Ｒ^４４は、それぞれ上記と同じ意味を表す。］ In addition, the dye (AI) can also be obtained by reacting the compound represented by the formula (BI) with the compound represented by the formula (C-III) in the presence of an organic solvent or without a solvent. It can also be manufactured.

[In formula (C-III), R ^{41 to} R ⁴⁴ each represent the same meaning as described above. ]

  The amount of the compound represented by the formula (CI) used in the reaction between the compound represented by the formula (BI) and the compound represented by the formula (CI) is represented by the formula (BI). Preferably they are 0.5 mol or more and 8 mol or less with respect to 1 mol of compounds represented, More preferably, they are 1 mol or more and 3 mol or less.

  The amount of the compound represented by the formula (C-II) used in the reaction between the compound represented by the formula (B-II) and the compound represented by the formula (C-II) is represented by the formula (B-II). Preferably they are 0.5 mol or more and 8 mol or less with respect to 1 mol of compounds represented, More preferably, they are 1 mol or more and 3 mol or less.

  The amount of the compound represented by the formula (C-II) used in the reaction between the compound represented by the formula (B-III) and the compound represented by the formula (C-II) is represented by the formula (B-III). Preferably they are 0.5 mol or more and 8 mol or less with respect to 1 mol of compounds represented, More preferably, they are 1 mol or more and 3 mol or less.

  The amount of the compound represented by the formula (C-III) used in the reaction between the compound represented by the formula (BI) and the compound represented by the formula (C-III) is represented by the formula (BI). Preferably they are 0.5 mol or more and 8 mol or less with respect to 1 mol of compounds represented, More preferably, they are 1 mol or more and 3 mol or less.

  From the viewpoint of yield, each of the above reactions is preferably performed in an organic solvent. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitrated hydrocarbon solvents such as nitrobenzene; methyl Ketone solvents such as isobutyl ketone; amide solvents such as 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent used is preferably 1 part or more and 20 parts or less, more preferably 1 part or less with respect to 1 part of the compound represented by the formula (BI), (B-II) or (B-III). 2 parts or more and 10 parts or less.

  The reaction temperature of each reaction is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

  From the viewpoint of yield, it is preferable to carry out the reaction in the presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride and the like. The amount of the condensing agent to be used is preferably 0.1 part or more and 20 parts or less with respect to 1 part of the compound represented by the formula (BI), (B-II) or (B-III). Preferably they are 0.2 part or more and 5 parts or less.

  As the method for taking out the dye (AI) from the reaction mixture after completion of the reaction, various known methods can be employed. For example, the dye (AI) can be taken out by mixing the reaction mixture with an alcohol (for example, methanol or the like) and collecting the precipitated crystals by filtration. It is preferred to add the reaction mixture to the alcohol. The temperature at which the reaction mixture is added is preferably −100 ° C. or higher and 50 ° C. or lower, more preferably −80 ° C. or higher and 0 ° C. or lower. Moreover, after mixing, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The compounds represented by the formulas (B-I), (B-II) and (B-III) are produced by a known method such as the method described in West German Patent Application P3928243.0, for example. Can do. The compounds represented by the formulas (C-I), (C-II) and (C-III) should be produced by a known method such as the method described in West German Patent Application P3926770.9. Can do.

  The dye (AI) has excellent spectral characteristics and can be used alone as a blue pigment for the blue filter layer.

［式（Ａ−ＩＩ）中、Ｘは、窒素原子またはＣＨを示す。Ｒ^４１は、水素原子または炭素数１〜４のアルキル基を示す。Ｒ^４２は、水素原子、シアノ基、カルバモイル基、カルボキシル基または炭素数１〜４のアルコキシカルボニル基を示す。Ｒ^４３は、酸素原子、Ｃ（ＣＮ）_２、Ｃ（ＣＮ）ＣＯＯＬ^１またはＣ（ＣＯＯＬ^１）_２を示し、Ｌ^１は、炭素数１〜８のアルキル基を示す。但しＬ^１がメチレン単位を有する場合には、該メチレン単位の１つまたは２つが酸素原子で置換されていてもよい。Ｒ^６１は、水素原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、炭素数１〜２０のアルキル基であって、該アルキル基を構成するメチレン基間に酸素原子が挿入されているアルキル基、または置換されていてもよいアリール基を表す。Ｒ^６２は、水素原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよいアミノ基、または置換されていてもよいアリール基を表す。Ｒ^６３は１つ以上のハロゲン原子を有する炭素数６〜２０のアリール基を表す。］ Here, among the dyes (AI), a compound represented by the following formula (A-II) is novel, and the compound represented by the formula (A-II) has good heat resistance. The colored photosensitive resin composition containing the compound represented by the formula (A-II) is excellent in heat resistance.
.

[In the formula (A-II), X represents a nitrogen atom or CH. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms. R ⁴³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents an alkyl group having 1 to 8 carbon atoms. However, when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom. R ⁶¹ is a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom, and an alkyl group having 1 to 20 carbon atoms, between the methylene groups constituting the alkyl group. It represents an alkyl group having an oxygen atom inserted therein or an aryl group which may be substituted. R ⁶² represents a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or an aryl group that may be substituted. R ⁶³ represents an aryl group having 6 to 20 carbon atoms having one or more halogen atoms. ]

［式（Ａ−ＩＩＩ）中、Ｒ^６４はハロゲン原子を表す。Ｒ^６５〜Ｒ^６７は、それぞれ独立して、水素原子、ハロゲン原子、アミノ基またはハロゲン原子で置換されていてもよい炭素数１〜２０のアルキル基、置換されていてもよいアミノ基、炭素数１〜２０のアルキル基であって、該アルキル基を構成するメチレン基間に酸素原子が挿入されているアルキル基、置換されていてもよいアリール基、あるいはヒドロキシル基を表す。Ｒ^６８は水素原子またはハロゲン原子を表す。］ In particular, a compound represented by the formula (A-II) in which R ⁶³ is a group represented by the formula (A-III) is preferable, and specifically, the compound is represented by the above formula (AI-6). Pigments.

[In the formula (A-III), R ⁶⁴ represents a halogen atom. R ^{65 to} R ⁶⁷ are each independently a hydrogen atom, a halogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or a carbon number. 1 to 20 alkyl groups each representing an alkyl group having an oxygen atom inserted between methylene groups constituting the alkyl group, an optionally substituted aryl group, or a hydroxyl group. R ⁶⁸ represents a hydrogen atom or a halogen atom. ]

  In order to adjust the color, that is, to adjust the spectral characteristics, other dye (A1), pigment (P), or a mixture thereof may be used in combination with dye (AI).

Examples of the dye (A1) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamides of acid dyes. of Dyers and Colorists)) and known dyes described in dyeing notes (Color Dyeing). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. C. such as Disperse Yellow 54, 76 I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be used alone or in combination of two or more.

［式（１）中、Ｒ¹及びＲ^２は、それぞれ独立に、置換基を有していてもよいフェニル基を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子はハロゲン原子で置換されていてもよく、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ¹及びＲ^３は、隣接する窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ^２及びＲ^４は、隣接する窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜４の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一であっても異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子と一緒に３〜１０員含窒素複素環を形成していてもよい。
Ｒ¹¹は、それぞれ独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］ Moreover, in the classification | category by a chemical structure, a xanthene dye is preferable and the compound represented by Formula (1) is more preferable.

[In Formula (1), R < ¹ > and R < ² > represents the phenyl group which may have a substituent each independently.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ³ may be combined with an adjacent nitrogen atom to form a ring containing a nitrogen atom, and R ² and R ⁴ may be combined with an adjacent nitrogen atom to form a ring containing a nitrogen atom. It may be formed.
R ⁵ _{is, -OH, -SO 3 H, -SO} 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ Represents.
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to form 3 to 10 members together with a nitrogen atom. A nitrogen-containing heterocycle may be formed.
R ¹¹ each independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and heptyl. Group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups having 1 to 20 carbon atoms; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group A branched alkyl group having 3 to 20 carbon atoms such as a group, neopentyl group or 2-ethylhexyl group; 3 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group or tricyclodecyl group ˜20 alicyclic saturated hydrocarbon groups.

Examples of —OR ⁸ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

Examples of —CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3 -Methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group; N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N , N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfa N, N-2 substituted sulfamoyl groups such as yl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, etc. Can be mentioned.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle together with the nitrogen atom. Examples of the heterocyclic ring include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ include those having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is -O -, - CO- or ^{-NR 11} - may be replaced by.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ⁶ and R ⁷ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert. -A butyl group, an isopentyl group, a neopentyl group, etc. are mentioned.

Examples of the aralkyl group having 7 to 10 carbon atoms representing R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, -SO 2 R ⁸ , —SO ₃ R ⁸ and —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among these substituents, —R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. -SO ₃ in this case ^- Z ^{+ _{The, -SO 3 - + N (R}} 11) 4 are preferred.

As R ³ and R ⁴ , an unsubstituted monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are preferable. Further preferred.

R ¹ and R ³ may be combined with an adjacent nitrogen atom to form a ring containing a nitrogen atom, and R ² and R ⁴ may be combined with an adjacent nitrogen atom to form a ring containing a nitrogen atom. It may be formed. Examples of the ring containing a nitrogen atom include the following.

The _{^{R 5, -SO 3 H, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred.
As R < ⁶ > and R < ⁷ >, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is more preferable.
m is preferably an integer of 0 to 2, and more preferably 0 or 1.

［式（２）中、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
ｐ及びｑは、それぞれ独立に、０〜５の整数を表す。ｐが２以上である場合、複数のＲ²³は同一でも異なってもよく、ｑが２以上である場合、複数のＲ²⁴は同一でも異なってもよい。］ As the compound (1), a compound represented by the formula (2) is preferable.

Wherein ^{(2), R 21, R} 22, R 23 and R ²⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.
p and q represent the integer of 0-5 each independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different. ]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ²¹ , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Groups and the like.
R ²¹ and R ²² are preferably each independently a methyl group or an ethyl group. R ²³ and R ²⁴ are preferably methyl groups.
m and n are preferably integers of 0 to 2, and are preferably 0 or 1.

［式（３）中、Ｒ³¹及びＲ³²は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。］
Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴を表す炭素数１〜４のアルキル基としては、前記と同じものが挙げられる。Ｒ³¹及びＲ³²は、それぞれ独立に、メチル基又はエチル基であることが好ましい。Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子又はメチル基であることが好ましい。 As the compound (1), a compound represented by the formula (3) is preferable.
Is preferred.

[In formula (3), R ³¹ and R ³² each independently represents an alkyl group having 1 to 4 carbon atoms.
R ³³ and R ³⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
Examples of the alkyl group having 1 to 4 carbon atoms representing R ³¹ , R ³² , R ³³ and R ³⁴ are the same as those described above. R ³¹ and R ³² are preferably each independently a methyl group or an ethyl group. R ³³ and R ³⁴ are preferably each independently a hydrogen atom or a methyl group.

  Examples of compound (1) include compounds represented by formula (1-1) to formula (1-7), respectively. Especially, the compound represented by Formula (1-1) is preferable at the point which is excellent in the solubility to an organic solvent.

で表される化合物と、式（1ｂ）で表される化合物及び式（1ｃ）で表される化合物

［式（１ｂ）及び式（１ｃ）中、Ｒ^１〜Ｒ^４は、それぞれ上記と同じ意味を表す。］
とを、有機溶媒の存在下又は無溶媒で反応させる方法が挙げられる。収率の点から、無溶媒で反応させることが好ましい。反応温度は、３０℃〜１８０℃が好ましく、８０℃〜１３０℃がより好ましい。反応時間は、１時間〜１２時間が好ましく、３時間〜８時間がより好ましい。 As a manufacturing method of a compound (1), Formula (1a)

A compound represented by formula (1b) and a compound represented by formula (1c)

[In formula (1b) and formula (1c), R ^{1 to} R ⁴ each represent the same meaning as described above. ]
And in the presence of an organic solvent or without solvent. From the viewpoint of yield, it is preferable to carry out the reaction without solvent. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol and butanol; nitrated hydrocarbon solvents such as nitrobenzene; methyl isobutyl Ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like.

The amount of the compound represented by the formula (1b) and the compound represented by the formula (1c) is preferably 1 mol or more and 8 mol or less with respect to 1 mol of the compound represented by the formula (1a). More preferably, it is 1 mol or more and 5 mol or less. Each may be allowed to react stepwise or simultaneously.
The compound represented by the formula (1b) and the compound represented by the formula (1c) are preferably the same compound in that the production of the compound (1) is easy.

  The method for obtaining the target compound (1) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with an acid (for example, acetic acid and the like), and the precipitated crystals can be collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

The pigment (P) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

  The pigment (P) is preferably a phthalocyanine pigment or a dioxazine pigment, more preferably C.I. I. At least one selected from the group consisting of CI Pigment Blue 15: 6 and CI Pigment Violet 23. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The pigments preferably have a uniform particle size.
The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

The content of the dye (AI) is preferably 1% by mass or more and 100% by mass or less, more preferably 10% by mass or more and 100% by mass or less, with respect to the total amount of the colorant (A).
When the dye (A1) is contained, the content thereof is preferably 0.5% by mass or more and 80% by mass or less, more preferably 40% by mass or more and 90% by mass or less, with respect to the total amount of the colorant (A). It is. When the pigment (P) is contained, the content thereof is preferably 35% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 70% by mass or less with respect to the total amount of the colorant (A). More preferably, it is 1 mass% or more and 50 mass% or less.
The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass with respect to the total amount of the solid content. % To 50% by mass. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

  In the present specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored photosensitive resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Alkali-soluble resin (B)>
The alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) is derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer containing structural units.
Examples of such a resin (B) include the following resins [K1] to [K6].
Resin [K1] at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and having 2 to 4 carbon atoms A copolymer of a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say.
(B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (II), and Formula (III) The compound etc. which are represented by these are mentioned.

[In Formula (II) and Formula (III), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

  Examples of the compound represented by the formula (III) include compounds represented by any one of the formulas (III-1) to (III-15). Among them, formula (III-1), formula (III-3), formula (III-5), formula (III-7), formula (III-9) or formula (III-11) to formula (III-15) A compound represented by formula (III-1), formula (III-7), formula (III-9) or formula (III-15) is more preferred.

  The compound represented by the formula (II) and the compound represented by the formula (III) may be used alone or in combination with the compound represented by the formula (II) and the compound represented by the formula (III). May be. When these are used in combination, the content ratio of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored photosensitive resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
It is more preferable that
When the ratio of the structural units of the resin [K1] is in the above range, the colored photosensitive resin composition is excellent in storage stability, developability when forming a colored pattern, and solvent resistance of the resulting color filter. Tend.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer. Examples of the solvent (E) for the colored photosensitive resin composition of the present invention include the solvents described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored photosensitive resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored photosensitive resin composition of the present invention. Therefore, the manufacturing process of the colored photosensitive resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored photosensitive resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored photosensitive resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the pattern obtained are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is respectively based on the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (c); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10 to 90 mol%
It is more preferable that

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5].
Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl (meth) acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Acrylic acid copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin in which glycidyl (meth) acrylate is added to a resin, a resin in which glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resin [K4] such as a resin to which a relate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / Resin such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) Examples thereof include a resin [K6] such as a resin obtained by reacting acrylic acid with a resin further reacted with tetrahydrophthalic anhydride.

The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored photosensitive resin composition is excellent in developability.
Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and remaining film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And the above-mentioned (a), (b) and (c).

  Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass with respect to the total amount of the solid content. is there.
Further, the content ratio of the resin (B) and the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

前記Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

Ｒ３〜Ｒ７が式（１）で使用されているので、Ｒ５３〜Ｒ５８に変更してください。
［式（ｄ５）中、Ｒ^５３〜Ｒ^５８は、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］ The biimidazole compound is, for example, a compound represented by the formula (d5).

Since R3 to R7 are used in formula (1), change to R53 to R58.
[In formula (d5), R ^{53 to} R ⁵⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4. , 4 ′, 5,5′-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazo (See, for example, JP-B-48-38403, JP-A-62-174204, etc.), Imidazole compounds in which the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group ( For example, see JP-A-7-10913. Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

  The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. Etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di Propylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N- methylpyrrolidone and the like are more preferable.

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of a coloring photosensitive resin composition, More preferably, it is 75-92 mass%. In other words, the solid content of the colored photosensitive resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass.
When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) .

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.) and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.

  When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002%, based on the total amount of the colored photosensitive resin composition. It is 0.005 mass% or more and 0.07 mass% or less more preferably. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored photosensitive resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored photosensitive resin composition>
The colored photosensitive resin composition of the present invention is used, for example, as necessary, as a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). , A leveling agent (F), a polymerization initiation assistant (D1), and other components can be mixed.
The pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored photosensitive resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
The compound (AI) is preferably prepared in advance by dissolving it in part or all of the solvent solvent (E). The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored photosensitive resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored photosensitive resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored photosensitive resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored photosensitive resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

According to the colored photosensitive resin composition of the present invention, a color filter with particularly high brightness can be produced.
The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

Synthesis example 1
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in a flask over about 5 hours using another dropping pump. It was dripped. After dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1) solution having a solid content of 43.5%. The obtained resin (B-1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

[Preparation of colored photosensitive resin composition]
Example 1
Colorant (A): 26 parts of a thiazole dye represented by the formula (A-I-1);
Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored photosensitive resin composition.

Comparative Example 1
A colored photosensitive resin composition was obtained by the method described in Example 1 of Patent Document 1.

[Production of color filters]
The colored photosensitive resin composition was applied onto a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), exposure was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 0.7 μm).

[Chromaticity evaluation]
About the obtained coloring pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE using the characteristic function of C light source (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 1.

Example 2
The following reaction was performed in a nitrogen atmosphere. After putting 29.2 parts of potassium thiocyanate and 160.0 parts of acetone into a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of o-chlorobenzoic acid chloride was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, after the reaction mass was ice-cooled, 35.1 parts of dibutylamine was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, the reaction mass was ice-cooled, and 27.4 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 28.4 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after the reaction mass was allowed to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, stirring was stopped and the mixture was allowed to stand for 30 minutes, whereby it was separated into an organic layer and an aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. Further, the pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 88.0 parts of a compound represented by the formula (BI-1). Yield 95%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 1000.0 parts of normal pentanol, 133.0 parts of 3-aminocrotonitrile and 250.0 parts of N-cyanoacetyl-N ′-(2-ethylhexanoyl) hydrazine were added. After the addition, the mixture was stirred for 2 hours with heating under reflux. Next, after adding 166.4 parts of zinc chloride, the mixture was further stirred for 4 hours while heating under reflux. Then, 225.0 parts of concentrated hydrochloric acid was added dropwise. After completion of dropping, normal pentanol was distilled off together with water vapor. The remaining suspension was suction filtered, and the residue was washed with water to obtain a pale yellow solid. Further, the pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 215.0 parts of a compound represented by the formula (C-II-1). Yield 71%

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 120.0 parts of the compound represented by the formula (C-II-1), 1200.0 parts of glacial acetic acid and 1200.0 parts of concentrated hydrochloric acid, and then at room temperature. Stir for 30 minutes. Next, after the reaction mass was ice-cooled, 28.5 parts of a 23% aqueous sodium nitrite solution was added and stirred for 3 hours to obtain a reddish brown suspension. After the obtained reddish brown suspension is filtered by suction. The residue was washed with water to obtain a reddish brown solid. Further, the reddish brown solid was dried at 60 ° C. under reduced pressure to obtain 120.0 parts of a compound represented by the formula (C-I-1). Yield 90%

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 86.0 parts of the compound represented by the formula (BI-1) and 53.5 parts of polyphosphoric acid, and then the formula (CI-1) 80.3 parts of a compound represented by the formula and 321.0 parts of isopropanol were added and stirred at 95 to 100 degrees for 3 hours. The reaction mass was then cooled to room temperature and diluted with 800 parts of methanol. The methanol solution was then cooled to −78 ° C. and stirred for 1 hour to obtain a dark blue suspension. The residue was washed with methanol to obtain a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 24.0 parts of a compound represented by the formula (AI-6). Yield 15%

0.35 g of the compound represented by the formula (AI-6) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.00). 028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 4.4 (arbitrary unit) at λmax = 602 nm.

[Preparation of colored photosensitive resin composition and color filter]
Example 3
Colorant (A): 26 parts of a compound represented by the formula (AI-6);
Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored photosensitive resin composition.

The colored photosensitive resin composition was applied onto a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), exposure was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.2 μm).

[Heat resistance evaluation]
The coating film of the obtained colored photosensitive resin composition was heated at 200 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). When measured, the color difference (ΔEab *) was 2.1. The coating film of the colored photosensitive resin composition obtained in Example 1 was heated at 200 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured by a colorimeter (OSP-SP-200; manufactured by OLYMPUS). ), The color difference (ΔEab *) was 10.1.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the coloring photosensitive resin composition which can manufacture a high brightness color filter.

Claims (9)

It contains a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and the colorant (A) is represented by the formula (AI). A thiazole dye represented by the formula (AI) is a compound represented by the formula (A-II), and the alkali-soluble resin (B) comprises an unsaturated carboxylic acid and an unsaturated compound. A colored photosensitive resin composition which is a copolymer containing a structural unit derived from at least one monomer (a) selected from the group consisting of carboxylic acid anhydrides.

[In the formula (AI), X represents a nitrogen atom or CH, R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁴² represents a hydrogen atom, a cyano group, a carbamoyl group, Represents a carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms, R ⁴³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents a carbon number 1 to 8 alkyl groups, and when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom, and R ^{44 to} R ⁴⁶ are each independently A hydrogen atom, an amino group or an alkyl group having 1 to 20 carbon atoms which may be substituted with a halogen atom, an amino group which may be substituted, or an alkyl group having 1 to 20 carbon atoms, Configure Alkyl group having an oxygen atom is inserted between the alkylene group, an optionally substituted aryl group or a hydroxyl group. ]

[In the formula (A-II), X represents a nitrogen atom or CH. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms. R ⁴³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents an alkyl group having 1 to 8 carbon atoms. However, when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom. R ⁶¹ is a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom, or an alkyl group having 1 to 20 carbon atoms, between the methylene groups constituting the alkyl group. It represents an alkyl group having an oxygen atom inserted therein or an aryl group which may be substituted. R ⁶² represents a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or an aryl group that may be substituted. R ⁶³ represents an aryl group having 6 to 20 carbon atoms having one or more halogen atoms. ] The colored photosensitive resin composition according to claim 1, wherein R ⁶³ is a group represented by the formula (A-III).

[In the formula (A-III), R ⁶⁴ represents a halogen atom. R ^{65 to} R ⁶⁷ are each independently a hydrogen atom, a halogen atom, an amino group or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or a carbon number. 1 to 20 alkyl groups each representing an alkyl group having an oxygen atom inserted between methylene groups constituting the alkyl group, an optionally substituted aryl group, or a hydroxyl group. R ⁶⁸ represents a hydrogen atom or a halogen atom. ]   The alkali-soluble resin (B) is a structural unit derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and cyclic ethers having 2 to 4 carbon atoms. The colored photosensitive resin composition according to claim 1 or 2, which is a copolymer comprising a structural unit derived from the monomer (b) having a structure and an ethylenically unsaturated bond.   The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the cyclic ether structure is an aliphatic polycyclic epoxy structure. The monomer (b) having a C2-C4 cyclic ether structure and an ethylenically unsaturated bond is selected from the group consisting of a compound represented by the formula (II) and a compound represented by the formula (III) The colored photosensitive resin composition according to claim 1, wherein the colored photosensitive resin composition is at least one kind of compound.

[In Formula (II) and Formula (III), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You can,
X ^b1 and ^{X b2} represents a single ^{bond, -R b3 -, * - R} b3 -O -, * - R b3 -S- or ^* -R b3 -NH- the stands,
R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms,
* Represents a bond with O. ]   The color filter formed with the colored photosensitive resin composition in any one of Claims 1-5.   A display device comprising the color filter according to claim 6. A compound represented by formula (A-II).

[In the formula (A-II), X represents a nitrogen atom or CH. R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴² represents a hydrogen atom, a cyano group, a carbamoyl group, a carboxyl group or an alkoxycarbonyl group having 1 to 4 carbon atoms. R ⁴³ represents an oxygen atom, C (CN) ₂ , C (CN) COOL ¹ or C (COOL ¹ ) ₂ , and L ¹ represents an alkyl group having 1 to 8 carbon atoms. However, when L ¹ has a methylene unit, one or two of the methylene units may be substituted with an oxygen atom. R ⁶¹ is a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms which may be substituted with an amino group or a halogen atom, or an alkyl group having 1 to 20 carbon atoms, between the methylene groups constituting the alkyl group. It represents an alkyl group having an oxygen atom inserted therein or an aryl group which may be substituted. R ⁶² represents a hydrogen atom, an amino group, or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or an aryl group that may be substituted. R ⁶³ represents an aryl group having 6 to 20 carbon atoms having one or more halogen atoms. ] The compound according to claim 8, wherein R ⁶³ is a group represented by the formula (A-III).

[In the formula (A-III), R ⁶⁴ represents a halogen atom. R ^{65 to} R ⁶⁷ are each independently a hydrogen atom, a halogen atom, an amino group or an alkyl group having 1 to 20 carbon atoms that may be substituted with a halogen atom, an amino group that may be substituted, or a carbon number. 1 to 20 alkyl groups each representing an alkyl group having an oxygen atom inserted between methylene groups constituting the alkyl group, an optionally substituted aryl group, or a hydroxyl group. R ⁶⁸ represents a hydrogen atom or a halogen atom. ]